Process and preparation for the manufacture of azo dyestuffs



Patented Feb'. .18, 194i PROCESS AND PREPARATION FOR THE MANUFACTURE OFAZO DYESTUFFS Albert Schmelzer, Cologne-Mnlheim, Germany,

a'ssignor to General Aniline & Film Corporation, a corporation ofDelaware No Drawing. Application October 17, 1939, Se-

rial No. 1938 299,810. In Germany October 26,

9 Claims. (c1. 8- 5) The present invention relates to a process andpreparations for the stuffs on thefiber. I v

In my copending application Ser. No. 242,575,

I filed November 26, 1938, I have described and claimed a process andpreparations for the manufacture of azo dyestufls. In that process azodyestuffs-are prepared from coupling com- I ponents and such ,diazoaminocompounds as contain water-solubilizing groups in the radical attachedto the amino-nitrogen and can be split oif into the diazo compound andthe amine by reduction in the alkalinity of the preparation, in thepresence of volatile oxygen-containing watersoluble organic, bases; bysimply applying heat in the presence of moisture the diazo aminocompound is decomposed with the formation of he. corresponding diaz'ocompound and coupling of the diazo compound with the coupling com- :0ponent takes place.

It has now been found that also in the known process and preparationsused for the manufacture of azo dyestufls in which the diazo compoundsare employed in the form of alkali metal antidiazotates commonly namednitrosamines, the bases used until now, namely fixed alkalies, such ascaustic soda lye, can-wholly or partially be replaced with the sameadvantage by oxygencontaining organic volatile with steam to warrantdevelopment of the dyestufi within the usual steaming period of about 3to 5 minutes.. pling components and aromatic nitrosamines, used for thepreparation of the azo dyestufi's, the 85 fixed alkalls are wholly orpartially replaced by volatile oxygen-containing organic bases, the abter treatment with an acid or the hanging in the air, which operationshad. been necessary until 'now for the production of the dyestuffs afterthe 40 steaming, is nolonger required, since the dyestuif is alreadyformed by expelling the volatile oxygen-containing: organic bases bymeans of steam.

Like in the mentioned copending application the oxygen-containingorganic bases must exhibit watersolubility besides volatility withsteam. Suitable bases of this kind are e. g.

Monoethylaminoethanol 5o Diethylaminoethanol N-propylaminoethanolDimethylaminoethanol DimethylaminobutanoneDiethylaminoethanol-methylether u N-hydroxyethylpyrolidine manufactureof azo .dye-.

bases which are suflicient'ly If in the mixtures of cou- In preparationsserving for the manufacture of dyestuffs in which the fixed alkalies areonly partially replaced by volatile oxygen-containing organic bases, thepermissible quantity of the fixed alkalies still present depends uponthe components used. This quantity of fixed alkalies may vary withinwide limits; it may be higher than is calculated for the formation ofthe naphtholate.

The coupling components suitable for the new process are the same ashitherto employed in the process of preparing azo dyestuffs on the fiberfrom nitrosamines serving to provide the diazo compounds in the process;such coupling components are e. g. the arylamides of fl-hydroxy- 1naphthoic acid or of o-hydroxycarboxylic acids of higher ring systems,or acylacetic acid arylamides, or keto-methylene compounds capable ofcoupling, these components being known as ice-color coupling components.

The process itself is also carried out in the usual manner by applyingto fibers to be dyed mixtures containing nitrosamines, couplingcomponents, volatile oxygen-containing organic bases, or volatile,oxygen-containing organic 25 bases and fixed alkalies, and the usualadditions and steaming the fiber thus printed or impregnated, usingneutral steam, without, however, after treating with an acid or hangingfor some time as hitherto. necessary. 30

In comparison with the known process in which coupling components,aromatic nitrosamines and fixed alkalies are used the new process yieldsprints of a better penetration and of fuller, more vivid and clearershades. 88

The following examples illustrate the invention without being restrictedthereto:

Example 1 Bleached cotton fabric is printed with the folo lowingprinting paste:

. Grams RapidFast Yellow G (SchuItZ FarbstOITtabellen, 7.Auflage, No.49) 40 Caustic soda lye 38 B 10 45 Turkey red oil 20 Diethylethanolamine7 Water 350 Neutral starch-tragacanth thickener 500 steamed for 5minutes in the Mather-Flatt, rinsed hot-and soaped at the boil. A fullgreenish-yellow is obtained.

Example 2 A crepe fabric of viscose artificial silk is printa m Example3 A mixed fabric of mercerized cotton and viscose artificial silk isprinted in the usual manner with a printing paste of the following com-15 position:

Grams Bis 4.4-acetoacetylamino-3.3-dimethy1- diphenyl 20 44.6% potassiumdiazotate of 1-amino-2- 2 methoxy chlorobenzene 18. 4

Diethylethanolamine 100 Turkey red oil 20 Water 341.6 Neutral starchtragacanth thickener 500 35 After steaming, rinsing and soaping a vividyellow print is obtained.

Example 4 A printing paste corresponding to that of Ex- 80 ample 1 whichcontains per kg. 21 grams of 1-(2'.3-hydroxynapthoylamino) 2methylbenzene, an equivalent amount of the sodium antidiazotate of1-amino-3-chlorobenzene, 4 grams of sodium hydroxide, 20 grams of Turkeyred oil 35 and 120 grams of diethylethanolamine, is printed on mercerizdcotton fabric and after drying steamed for 4 minutes in the Mather-Platt. A full orange is obtained.

When using Rapid Fast Orange RG (Schultz Farbstoiftabellen 'l.AuflageNo. 52) and printing with the same quantity of diethylethanolamine abeautiful yellowish-orange is obtained.

Example 5 45 A fabric which consists in the warp of mer-' cerized cottonand in the woof of viscose artificial silk, is printed with a printingpaste containing per kg. 21 grams of1-(2.3'-hydroxynaphthoylamino)-2-ethoxybenzene, the equivao lent amountof the potassium anti-diazotate of 1- amino-2-methyl-5-chlorobenzene,4.2 grams of sodium hydroxide, 20 grams of Turkey red oil and 120 gramsof diethylethanol-amine. The printed fabric is dried, steamed for 5minutes 5 in the Mather-Flatt, rinsed in the heat and soaped. A vividscarlet is obtained.

Example '6 When using instead of the printing paste of 50 Example 5 aprinting paste which contains 1-(2'.3'-hydroxynaphthoylamino)- 4-methoxy- 2-methylbenzene and the nitrosamine from 1-amino-2-methy1-4-ch1orobenzene, and proceeding in the same manner abeautiful bluish-red print is obtained.

Example 7 A crepe fabric of viscose artificial silk is printed with apaste containing per kg. 21 grams 70 of 1-(2.3'-hydroxynapthoylamino)-2-methoxybenzene, an equivalent quantity of the antidiazotate from1-amino-2-meth0xy-5-chlorobenzene, grams of caustc soda lye 38 B., gramsof Turkey red oil and 80 grams of di- 15 ethylethanol-amine. Afterdrying the printed fabric is steamed for 5 minutes in the Mather- Platt,rinsed in the heat and soaped at the boil.

A full bluish-red is obtained.

Example 8 5 When using 1-(2'.3-hydroxynaphthoylamino) -3-nitrobenzeneinstead of the arylide of Example 7 and proceeding otherwise in the samemanner a wine-red is obtained.

Example 9 A fabric consisting of pure staple fiber is printed with apaste containing per kg. 21 grams of 1,- (2.3-hydroxynaphthoylamino) -2methylbenzene, the equivalent amount of the nitrosamine 15 sodium saltof 1-amino-5-trifiuoromethyl-2- ethylsulfonylbenzene, 2 grams of sodiumhydroxide and 120 grams of diethylethanol-amine. After drying theprinted fabric is steamed. for 5 minutes in the Mather-Platt, rinsed inthe heat 20 and soaped at the boil. A vivid golden-orange is obtained. I

Example 10 When using instead of the arylide and nitrosamine of Example9 1-(2.3'-hydroxynaphthoy1- amino) -2.5-dimethoxybenzene and thenitrosamine sodium salt of 1-amino-2.5-dichlorobenzene and proceedingotherwise in the same manner a vivid red-brown is obtained.

Example 11 A bleached cotton fabric is printed with a paste containingper kg. 21 grams of 1-(3-hydroxydiphenylene oxide-2'- carboylamino) 2.5

Example 12 A bleached cotton fabric is printed with the followingprinting paste:

' Grams Rapid Fast Blue B (Schultz Farbstofitabellen 7. Auflg. No. 490)50 65 Caustic soda lye 38 B 10 Turkey red oil 20 Dimethylethanol-amine80 Water 340 Starch tragacanth thickener 500 After drying the printedfabric is steamed for. 3 minutes in the Mather-Flatt, rinsed in the heat'and soaped at the boil. A navy-blue print is obtained.

Example 13' A bleached cotton fabric is printed with the followingprinting paste:

' Grams Rapid Fast Blue B (Schultz Farbstofftabellen '7. Auflg. No. 490)50 Turkey red oil 20 N-oxethylpyrrolidine Water 310 Starch tragacanththickener 500 7;

Example 14 Bleached cotton piece goods are printed with a paste of thefollowing composition:

- Grams 1-benzoacetylamino-4-benzoylamino-2.5 dimethoxy-benzene 20 44.6%potassium anti-diazotate from l-amino-2-methoxy-5-chlorobenzene 17Diethylethanol-amine 100 Anhydrous sodium carbonate 10 Turkey red oil 20Water 333 Neutral starch tragacanth thickener 500 The goods are dried,steamed for 5 minutes in the Mather-Flatt, rinsed and soa'ped. A vividfull golden-yellow print is obtained.

Example 15 Example 16 Mouseline-laine is printed with the followingprinting paste:

Grams A mixture of the nitrosamine from l-amino-2-methyl-4-chlorobenzene with l-acetoacetylamino-2.5-dimethoxy-4chloroben zene 60 Diethylaminoethanol 100 Water 240 Senegal gum (1,:1)600 The print is steamed for soaped at 60 5 minutes, rinsed and C. Aclear yellow is obtained.

droxynaphthoylamino) -2-ethoxybenzene..- DiethylaminoethanoL Water 220Senegal gum (1:1) 60 3 The print is steamed for 5 minutes, rinsed andsoaped at 60-80 C. An orange is obtained.

Example 18 According to Example 17 a printing paste is preparedcontaining 80 grams of a mixture of the nitrosamine from1-amino-2-methyl-5-chlorobenzene with 1 (2'.3 hydroxynaphthoyl amino)-2-ethoxybenzene. On -woo1 or weighted or unweighted natural silkscarlet prints are obtained.

Example 19 Weighted natural silk is printed with a printing pasteprepared according to Example 17 from 80 grams of a mixture of thenitrosamine from 1 -amino 2 methyl 5 chlorobenzene 'with 1 (2'.3'hydroxynaphthoylamino) 2 methylbenzene. After steaming, rinsing andsoaping at 60-80" C. a clear red is obtained.

I claim:

1. In the'process of preparing azo dyestuiis on the fiber from couplingcomponents and alkali metal anti-diazotates dissolved in fixed. alkalisthe improvement which consists in replacing the fixed alkalissubstantially by oxygen-containing, water-soluble organic nitrogenousbases volatile with steam and. developing the dye-stuffs by simplyapplying heat and moisture.

2. The process as claimed in claim 1 wherein the development is eifectedby steaming.

3. The process as claimed in claim 1 wherein as volatile,oxygen-containing, water-soluble organic bases such bases are employedas contain hydroxyalkyl groups.

4. The process as as volatile, oxygen-containing, water-soluble organicbases such bases are employed as contain oxethyl groups.

5. The process as claimed in claim 1 wherein diethylaminoethanol isemployed as volatile, oxygen-containing, water-soluble organic base.

6. The dye compositions comprising ice-color coupling components andalkali metal diazotates dissolved to an alkaline reacting solutionsubstantially in oxygen-containing, water soluble organic nitrogenousbases volatile with steam.

7. The preparations as claimed in claim 6 wherein as volatile,oxygen-containing, watersoluble organic bases such bases are employed ascontain hydroxyalkyl groups.

8. The preparations as claimed in claim 6 wherein as volatile,oxygen-containing, watersoluble organic bases such bases are employed ascontain oxethyl groups.

9. The preparations as claimed in claim 6 wherein diethylaminoethanol isemployed asvolatile, oxygen-containing, water-soluble organic base.

ALBERT SCHMELZER.

35 claimed in claim 1 wherein

